Bis[p-(2, 3-epoxypropoxy)phenyl]polycyclic saturated hydrocarbons and synthetic resinous polyethers thereof



Patented Nov. 12, 1968 3,410,825 BIS[p (2,3 EPOXYPROPOXY)PHENYL]POLY-'CYCLlC SATURATED HYDROCARBONS AND SYNTHETIC RESINOUS POLYETHERS THEREOFHarry W. Coover, Jr., and Richard L. McConnell, Kingsport, Tenn.,assignors to Eastman Kodak Company, Rochester, N.Y., a corporation ofNew Jersey No Drawing. Continuation-impart of application Ser. No.480,774, Aug. 18, 1965. This application Feb. 27, 1967, Ser. No. 619,035

The portion of the term of the patent subsequent to Jan. 17, 1984, hasbeen disclaimed 13 Claims. (Cl. 260-47) ABSTRACT OF THE DISCLOSURE Newcompounds are provided having the formula:

or the formula:

in which A is a nuclearly attached monovalent radical having two, threeor four fused rings, each ring consisting of five carbon atoms connectedby single bonds and in which B is a nuclearly attached divalent radicalhaving three or four fused rings, each ring consisting of five carbonatoms connected by single bonds and X and X are each hydrogen, methyl orhalogen.

Also, there are provided new synthetic resinous polyethers composedessentially of recurring units derived from at least one of the abovecompounds and which may include copolymers wherein the comonomer is aknown bisphenol or bifunctional glycol. The copolymers can be random orblock copolymers.

CH3 n are known in the art. (Such polyethers are distinct from theso-called Epon resins which are of lower molecular weight, containterminal epoxy groups and require chemical curing. The chemical curingcauses cross-linking so that the Epon resins are not thermoplastic)These compounds are useful in a wide variety of applications. Thus, theymay be used for injection molding, extrusion and blow molding and foradhesives and coatings. The presence of secondary hydroxyl groupspermits chemical cross-linking with such materials as isocyanates,anhydrides, etc., when resistance to solvents is desired. However, thesepolyethers suffer two major disadvantages, namely low sofetening pointand flammability. Since such polyethers soften at about C., moldedobjects made from them are deformed quite badly when an attempt is madeto sterilize them with steam. Also, due to their high flammability,large amounts of antimony oxide and/or chlorinated compounds must beblended with such resins to provide some degree of flame resistance.This is itself disadvantageous since the presence of antimony andchlorine compounds cause stability problems, embrittle the resin andrender it opaque.

It is an object of this invention to provide certain newbis[p-(2,3-epoxypropoxy)phenyl]polycyclic saturated hydrocarbons andsynthetic resinous polyethers thereof.

It is another object of this invention: to provide thermoplasticpolyether resins having high stiffness, good clarity, a heat distortiontemperature sufliciently high to permit steam sterilization of moldedobjects, and flame resistance.

These, and other objects, are attained by the practice of this inventionwhich, briefly, comprises providing a high melting, high molecularweight polyether composed essentially of recurring units having theformula ?11 "CH2CHCH20 X"O in which at least 10 mole percent of theradical X- is the divalent radical remaining after removal of theterminal hydroxyl groups from a bisphenol having the for- K CH; l

the hexahydro-4,7-methanoindanylidene group thehexahydro-4,7-methanoindanylmethylene groups (To 0g and CH2 v i themethylno'rcamphanylmethylene groups 4 CH/ CH,

3,410,825 3 4 the decahydro-1,4,5,S-dimethanonaphthylidene group Thenovel compounds of this invention may be prepared by reacting adiglycidyl ether of one of the previ- 1 ously described bisphenols witha bisphenol. Such a reac- CH2 CH2 tion is exemplified by the followingequation:

lO-QfiQ-OCHzZiCH or the decahydro-1,4,5,8-dimethanonaphthylmethyleneAlternatively, the polyethers of this invention may be group prepared byreacting the bisphenol with epichlorohydrin OH in the presence of abase. Such a reaction is illustrated by CH: CH, 25 the followingequation:

-OH o-Q Q-oomouom NaOH Q CHz-CHOHC1 OH i I CH: 1 OH 0 Copolyethers maybe prepared for example, by reacting one of the bisphenols with adiglycidyl ether of a different dihydroxy compound as illustrated below:

and

omr luomo H I H oomonoHm-Q -0- OH; CH; 5

The reactions may be conducted either in the presence or absence ofinert solvents. Operable reaction temperatures range from about 25 C. toabout 300 C. while the preferred reaction temperatures include 25 C. toabout 225 C. The reactions are base catalyzed and typical catalystsinclude sodium phenoxide, potassium phenoxide, lithium phenoxide, sodiummethoxide, potassium methoxide, lithium methoxide, sodium isobutoxide,aluminum isopropoxide, lithium amide, tributylamine, sodium hydroxide,sodium silicate, etc.

Some examples of bisphenols as defined by the above formula which may beincorporated into the polyethers of this invention include:

4,4-(2-norcamphanylidene) diphenol, M.P. 140-190 C. (The MP. depends onthe rate of heating and loss of water of hydration.)

4,4-(hexahydro-4,7-methanoindan-S-ylidene) diphenol monohydrate, M.P.22l-223 C.

4,4'-(hexahydro-4,7-methanoindan-S-ylidene) di-ocresol, M.P. 208-210 C.

4,4'-(3-methylnorcamphan-Z-ylmethylene) diphenol,

M.P. 222-224 C.

Other 'bisphenols falling within the category represented by the abovestructural formula and useful for incorporation into the new polyethersof this invention are:

4,4'-(hexahydro-4,7-methanoindan-5-ylidene) di-mcresol4,4'-(3-methylnorcamphan-Z-ylmethylene) di-o-cresol4,4'-(2-methylnorcamphan-2-ylmethylene) diphenol4,4'-(Z-methylnorcarnphan-Z-ylmethylene) di-o-cresol4,4'-(3-methyl-2-norcamphanylidene) diphenol4,4'-(3-methyl-2-norcamphanylidene) di-o-cresol4,4'-(2-norcamphanylidene) di-o-cresol4,4-(decahydro-1,4,5,8-dimethanonapth-2- ylmethylene) diphenol4,4'-(decahydro-l,4,5,8-dimethanonaphth-2- ylmethylene) di-o-cresol4,4-(decahydro-1,4,5,S-dimethanoriaphth-2-ylidene) diphenol4,4-(decahydro-1,4,5,8-dimethan0naphth-Z-ylidene) di o-cresol4,4-(hexahydro-4,7-methanoindan-2-ylmethylene) diphenol4,4-(hexahydro-4,7-methanoindan-Z-ylmethylene) di-o-cresol4,4-(hexahydro-4,7-methanoindan-2-ylidene) diphenol4,4'-(hexahydro-4,7-methanoindan-2-ylidene) di-o-cresol Such bisphenolsare readily prepared in 70-90% yields by treating the appropriate ketoneor aldehyde with phenol or cresol in the presence of hydrochloric acidand beta-mercaptopropionic acid. The preparation of a typlcal compound,4,4-(2 norcamphanylidene) diphenol, W111 serve to illustrate the generalprocedure which may be employed for preparing any of the above-mentionedbisphenols.

A mixture containing 55 g. (0.50 mole) of norcamphor, 188 g. (2.0 moles)of phenol, 125 g. of concentrated hydrochloric acid, and 2.5 g. ofbeta-mercaptopropionic acid was stirred at 25 C. for 48 hours. The loweraqueous layer was decanted from the upper semisolid organic layer. Theorganic layer was washed twice with 500 ml. of hot water (70-80 C.) toremove the excess phenol. The crude yield was 127-140 g. (85-94%calculated as the monohydrate). The crude bisphenol melted in the140--190 C. range depending upon the rate of heating and loss of waterof hydration. The compound 4,4-(2- norcamphanylidene) diphenol, can berecrystallized from mixtures of acetic acid and water, or isopropanoland water.

When a diglycidyl ether of one of the above-mentioned bisphenols is tobe used as one of the starting materials for the preparation of thepolyethers of this invention, it may be prepared by treating the'bisphenol with epichlorohydrin or epibromohydrin in the presence ofsodium hydroxide. This reaction may be illustrated by the followingequation in which 4,4'-(2-norcamphanylidene) bisphenol is reacted withepichlorohydrin to give 2,2-bis-[p-(2,-3-epoxypropoxy)phenyl]norcamphane.

In carrying out this reaction, it is preferable to employ a slightexcess of epichlorohydrin or epibromohydrin although stoichiometricamounts of the reagents may be employed if desired. The reaction can beeffected at a temperature of 25 to 125 C., and continued for a period of1 to 8 hrs. Although solvents are not required for this reaction,various inert solvents such as diethyl ether, dibutyl ether, toluene,xylene, benzene, esters such as ethyl acetate, butyl acetate, isobutylacetate, ethyl isobutyrate and isobutyl iso'butyrate may be employed ifdesired. The advantage to be obtained by the employment of such solventsis merely a fluid reaction mixture.

Described below are some preparations of diglycidyl ethers ofbisphenols, which compounds may be used as one of the starting materialsfor the preparation of the polyethers of this invention:

Preparation of 2,2-bis[p(2,3-epoxypropoxy)phenyl] norcamphaneEpichlorohydrin (37 g., .4 mole), 4,4'-(2-norcamphylidene) diphenolmonohydrate (29.8 g., .1 mole) were placed in a 300 ml. flask andstirred with a high-speed stirrer. The reaction mixture was heated to 70and 16 g. of a 50% sodium hydroxide solution was added dropwise over a20-minute period. The reaction was exothermic and the temperature roseto C. for a short period of time. Ten ml. of water was added and thenthe reaction mixture was heated for 3 /2 hr. in the 70-90 C. range.After cooling the reaction mixture, 200 ml. of ether was added andstirred well. The aqueous solution was drained off and the ethersolution was washed three times with water. After drying the ethersolution over sodium sulfate, the ether was stripped off on the steambath at atmospheric pressure. Finally, the product was stripped in vacuoto a pot temperature of 50 C. and a pressure of 2 mm. The product is anextremely viscous, straw-colored material and amounted to 41.4 g. It hadan oxirane oxygen content of 6.2%.

Preparation of 5,5-bis[p-(2,3-epoxypropoxy)phenyl]hexahydro-4,7-methanoindane This extremely viscous product was preparedfrom 4,4- (hexahydro 4,7 methanoindan-S-ylidene)diphenol,epichlorohydrin and aqueous sodium hydlromide, according to thepreviously described procedure. It had an oxirane oxygen content of6.7%.

Preparation of2,2-bis[4-(2,3-epoxypropoxy)-3-methylphenyl]hexahydro-4,7-methanoindaneThis diepoxide was prepared from 4,4'-(hexahydro-4,7-methanoindan-5-ylidene)di-o-cresol, epibromohydrin, and aqueouspotassium hydroxide according to the previously described procedure. Theoxirane oxygen content was 5.9%.

7 Preparation of 2-bis[p-(2,3-epoxypropoxy)phenyl]methylene-3-methylnorcamphane This viscous material was prepared from4,4-(3- methylnorcamphan 2 ylmethylene)diphenol, epichlorohydrin andaqueous sodium hydroxide according to the previously describedprocedure. The oxirane oxygen content was 6.8%.

As previously mentioned, copolyethers may be prepared by reacting one ofthe previously described bisphenols with a diglycidyl ether of adifferent dihydroxy compound. If the different dihydroxy compound is notone of the bisphenols previously described, then it should comprise nomore than 90 mole percent, and preferably no more than 75 mole percent,of the total amount of dihydroxy reactant, and the bisphenol previouslydescribed should comprise at least mole percent, and preferably at least25 mole percent, of this total.

Examples of other dihydroxy compounds which may be incorporated into thepolyethers of this invention include Bisphenol A, hydroquinone andvarious glycols. The diglycidyl ethers of these compounds may be reactedwith one of the previously described bisphenols.

Aliphatic or glycol diglycidyl ethers may be prepared by epoxidizingdiallyl ethers of saturated hydrocarbon glycols in which the hydroxygroups are separated by more than two carbon atoms by treatment with anepoxidizing agent such as peracetic acid, hydrogen peroxide, performicacid or hypochlorous acid. Described below are the preparations of somealiphatic diglycidyl ethers which may be used in the preparation ofcopolyethers included in this invention:

Preparation of 1,4-bis(2,3-epoxypropoxymethyl) cyclohexane1,4-bis(allyloxymethyl)cyclohexane (0.5 mole) and sodium acetate (0.5mole) were placed in 300 ml. of chloroform and stirred while peraceticacid (1.2 mole) (40% peracetic acid in acetic acid) was added dropwise.The reaction was exothermic and the temperature rose to about 60 C. Thenthe reaction mixture was stirred for four hours at 25 C. After dilutingthe reaction mixture with water, it was extracted with diethyl ether.The ether solution was washed with saturated sodium thiosulfate solutionand then again with water. After drying the organic solution over sodiumsulfate, the solvents were removed by distillation at atmosphericpressure. Finally, the product was stripped in vacuo (1 mm.) leaving theproduct as a transparent viscous oil. The oxirane oxygen content of thiscompound was 11.4%.

Preparation of 1,3-bis (2,3-epoxypropoxy)-2,2-

dimethylpropane This viscous oil was prepared from 1,3-bis(allyloxy)2,2-dimethylpropane and peracetic acid according to the previousprocedure. The oxirane oxygen content of this compound was 13.5%.

Preparation of 1,3-bis(2,3-epoxypropoxy)2,2,4,4- tetramethylcyclobutaneThis compound was prepared from 1,3-diallyloxy-2,2,4,4-tetramethylcyclobutane and peracetic acid according to theprevious procedure. The oxirane oxygen content of this compound was10.9%.

Preparation of 1,3-bis(2,3-epoxypropoxy)-2,2,4- trimethylpentane Thiscompound was prepared from 1,3-diallyloxy-2,2,4- trimethylpentane andperacetic acid according to the previous procedure. The oxirane oxygencontent of this compound was 10.2%.

Preparation of 2,5-(or 6-)bis(2,3-epoxypropoxymethyl) norcamphane Thisviscous transparent oil was prepared from 2,5-(or 6-)bis(allyloxymethyl)norcamphane and peracetic acid according to theprevious procedure. The oxirane oxygen content of this compound was10.3%.

Preparation of l,4-bis(2,3-epoxya2rmethylpropoxymethyl) -cyclohexaneThis compound was prepared from 1,4-bis(methallyloxymethyl) cyclohexaneand peracetic acid according to the previous procedure. The oxiraneoxygen content of this compound was 9.6

The polymers of this invention are characterized by high softeningpoints which permit molded objects made from the polymers to be steamsterilized without distortion of the object. They may be prepared havingvarying molecular weights. In order to produce molded objects with goodphysical properties, polymers with molecular weights greater than 10,000are desirable and molecular weights of 20,000 to 50,000 or even highersuch as 100,000 are preferred.

The polyethers of this invention may be processed into molded objects byconventional injection molding, compression molding or extrusiontechniques. Prior to molding, conventional stabilizers, anti-oxidants,plasticizers, pigments, etc., may be incorporated into the polyethers.

The following examples illustrate the best modes contemplated forcarrying out this invention:

EXAMPLE 1 2,2 bis[p (2,3 epoxypropoxy)phenyl]norcamphane (0.02 mole),4,4-(2-norcamphanylidene)diphenol (0.021 mole) and sodium phenoxide(0.01 g.) were reacted at C. with stirring under an atmosphere of N for1 hr. The temperature was gradually raised to 190-200 C. and maintainedthere for 0.5 hr. The polymer melt was clear and extremely viscous. Thesoftening point of the polymer was 200 C. and it had a melt flow of 0.4(determined at 230 C./ 2.16 kg. weight). The resulting product wascomposed essentially of recurring ether units having the formula:

Buttons compression molded from the polymer were clear, hard andextremely stiff.

EXAMPLE 2 A polyether having the same structure and properties wasprepared by treating 4,4-(2-norcamphanylidene)diphenol with an equimolaramount of epichlorohydrin in the presence of aqueous sodium hydroxide.

EXAMPLE 3 2,2 bis[3,5 dichloro 4 (2,3-epoxypropoxy)phenyl]norcamphane,M.P. 158-162 C. (0.03 mole), and 4,4 (2 norcamphanylidene)bis[2,6dichlorophenol] 0.0.031 mole) were reacted according to the generalprocedure of Example 1 except that sodium methoxide was the catalyst andthe final reaction temperature was 225 C. A compression molded plate washard, stiff and quite flame resistant. The softening point of thispolymer was about 220-240 C. It was composed essentially of recurringunits having the formula:

([31 C1 ---0@ --OCH:CH(|)H:

OH 01 CH: Cl

EXAMPLE 4 By the process described in Example 1, 2,2-bis[p-(2,3-epoxypropoxy)phenyl]norcamphane) 0.02 mole) and 4, 4(2-norcamphanylidene)bis[2,6-dichlorophenol] (0.02

mole) were reacted using potassium phenoxide as the catalyst. Specimensmolded from the product were clear, hard and flame resistant. Theproduct was composed essentially of recurring units having the formula:

4,7-methanoindane (0.005 mole) and 4,4-hexahydro-4,7- methanoindan 5ylidene) diphenol (0.005 mole) were added and the reaction was completedat 210 C. A molded button from this copolymer was stiff and hard.

EXAMPLE 5 By the process described in Example 4, 2,2-bis[p-(2,3-epoxypropoxy)phenyl]norcamphane (0.02 mole), 4,4-(2-norcamphanylidene)diphenol (0.01 mole) and 4,4- (2-norcamphanylidene)bis[2,6-dichlorophenol] (0.01 mole) were reacted toobtain a high melting, flame resistant copolymer.

EXAMPLE 6 By the process described in Example 1, 1,3 bis(2, 3epoxypropoxy)2,2,4,4 tetramethylcyclobutane (0.04 mole) and 4,4 (2norcamphanylidene) diphenol 0.04 mole) were reacted to obtain a highmelting copolyrner composed essentially of recurring units having theformula:

CH3 CH3 --CH:CHCH:O H

H oomonorn- Q-oon: CH3

EXAMPLE 7 A series of high melting copolymers were prepared by repeatingthe process of Example 6 substituting for the 1,3 bis(2,3epoxypropoxy)2,2,4,4 tetramethylcyclobutane equimolar amounts of each ofthe following:

1,3-bis 2,3-epoxypropoxy -2,2-dimethylpropane, 1,4-bis 2,3-epoxypropoxymethyl cyclohexane,

1,3-bis 2,3-epoxypropoxy -2,2,4-trimethylpentane and 2,5 -bis2,3-epoxypropoxymethyl norcamphane.

EXAMPLE 8 A series of flame resistant copolymers were prepared byrepeating the processes of Examples 6 and 7 substituting for the 4,4 (2norcamphanylidene) diphenol equimolar amounts of each of the following:

4,4-(2-norcamphanylidene)bis[2,6-dichloropheno1] and4,4-(2-norcamphanylidene)bis[2,6-dibromophenol] EXAMPLE 9 2,2-bis[p (2,3epoxypropoxy)phenyl] norcamphane (0.05 mole), 4,4'-(2-norcamphanylidene)diphenol (0.04 mole) and sodium phenoxide 0.01 g.) were reacted at 150C. with stirring under an atmosphere of N for 1 hr. Then,5,5-bis[p2,3-epoxypropoxy)phenyl]hexahydro- The product was a blockcopolymer containing structural units having the formula:

o -ooH,oHoH=- H CH:

and

O OCH:CHCH2- ()H OH;

EXAMPLE 10 A l-liter, 3-necked flask was charged with the following:

Bisphenol A (0.375 mole; 87.65 g.), 4,4-(2-norborny1idene)diphenolhydrate (0.125 mole; 37

The mixture was stirred overnight at room temperature, a solution of 3g. of NaOH in 12 ml. of water was added and the mixture was brought toreflux. Monochlorobenzene was added to the refluxing mixture, 30 ml.after 30 minutes reflux, 15 ml. additional after 45 minutes reflux andan additional 15 ml. after 60 minutes reflux. The mixture was thenrefluxed for 4 hours and a mixture of 4.8 g. of phenol dissolved in 30m1. of monochlorobenzene was added. After an additional 2 hours reflux,the reaction mixture was washed with 3 200-ml. portions of water. Then,200 ml. chloroform and a solution of 10 ml. of H PO in 50 ml. of waterwas added. This mixture was then washed with 8 200-ml. portions ofwater. The resulting viscous product was heated in a vacuum oven toremove most of the solvent and the residue was dissolved in dioxane.This solution was precipitated into cold water and the white product wasdried in an air oven. The final product weighed 144 g. (94% yield) andhad a melt fl'oW of 23. The plastic -was clear and flexible and had amelting point of 168 175 C. The product was a copolymer containing 75mole percent of Bisphenol A and 25 mole percent of 4,4-(2-norbornylidene) diphenol.

EXAMPLE 1 l the reaction is completed at 210 C. This block copolymercontains structural units having the formula:

and

OH Cl CH1 1 It is readily molded into buttons and plates which are flameresistant.

EXAMPLE 12 2-bis [p- (2,3-epoxypropoxy phenyl] methylene3-methylnorcamphane (0.1 mole), 4,4-3-methylnorcamphane-2-ylmethylene)diphenol (0.09 mole) and sodium methoxide (0.01 g.) arereacted at 155 C. with stirring under an amtosphere of N for 1 hr. Then2,2,4 ,4-tetramethylcyclobutanediol (0.02 mole) and1,3-bis(2,3-epoxypropoxy-Z,2,4,4-tetramethylcyclobutane (0.02 mole) areadded and the reaction is completed at 215 C. This block copolymercontains structural units having the formula:

H O H -C H, CH2 b and C H: C H:

H OCILCHCHa- C H: H! H EXAMPLE 13 5,5 bis[p(2,3-epoxypropoxy)phenyl]hexahydro-4,7- methanoindane (0.1 mole),4,4-(hexahydro-4,7-methanoindan-S-ylidene)diphenol (0.1 mole) and sodiumphenoxide (0.02 g.) are reacted at 150 C. with stirring under anatmosphere of N for 1 hr. Then Bisphenol A (0.02 mole) and2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane (0.02 mole) are added and thereaction is completed at 210 C. This block copolymer contains structuralunits having the formula:

2,2 bis[p (2,3 epoxypropoxy)phenyl]norcamphane (0.1 mole),4,4'-(2-norcamphanylidene)diphenol (0.1 mole), and sodium phenoxide(0.02 g.) are reacted at 150 C. with stirring under an atmosphere of Nfor 1 hr. Then 4,4 (decahydro-1,4,5,S-dimethanonaphthylidene) 1 2diphenol (0.04 mole) and 2,2-bis[p-(2,3-epoxypropoxy) phenyl]decahydro1,4,5,8-dimethanonaphthalene (0.04 mole) are added and the reaction iscompleted at 220 C. This block copolymer contains structural unitshaving the formula:

and

-o Q-oomouomla a It is readily molded into buttons and plates.

EXAMPLE 15 2,2 bis[p (2,3-epoxypropoxy)phenyl]norcamphane (0.1 mole),4,4'-(2-norcamphanylidene)diphenol (0.1 mole) and sodium phenoxide (0.01g.) are reacted at C. with stirring under an atmosphere of N for 1 hr.Then 4,4-(2-norcamphanylidene)bis[2,6-dibromophenol] (0.015 mole) and2,2-bis[3,5-dibromo-4-(2,3-epoxypropoxy)phenyl]norcamphane (0.015 mole)are added and the reaction is completed at 215 C. This block copolymercontains structural units having the formula:

and

I OH

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations and modifications can be elfected within the spirit and scopeof the invention as described hereinabove, and as defined in theappended claims.

We claim:

1. A compound having the formula:

or the formula:

in which A is a nuclearly attached monovalent radical having two, threeor four fused rings, each ring consisting of five carbon atoms connectedby single bonds and in which B is a nuclearly attached divalent radicalhaving three or four fused rings, each ring consisting of five carbonatoms connected by single bonds and X and X are each hydrogen, methyl orhalogen.

2. A compound as defined by claim 1 which is 5,5-bis[p-(2,3-epoxypropoxy)phenyl]hexahy-dro-4,7 methanoindane.

3. A compound as defined -by claim 1 which is 2,2-bis[4-(2,3expoxypropoxy)-3-methylphenyl1hexahydm 4,- 7-methanoindane.

4. A compound as defined by claim 1 which is Z-bis [p (2,3epoxypropoxy)phenyl]mcthylene-3-methylnorcamphane.

5. A synthetic resinous polyether composed essentially of recurringunits having the formula:

OH -OHz-HCHzO-XO in which from about 10 to 100 mole percent of theradical X is the divalent radical remaining after the removal of thetenminal hydroxyl groups from a bisphenol having the formula:

maximum-Q or the formula:

ore

in which R and R when taken collectively with the connecting carbon atomC are cyclohexyl or methylor halogensubstituted cyclohexyl, and when Rand R are taken separately are hydrogen, lower alkyl, cyclohexyl,methylor halogensubstituted cyclohexyl, phenyl, methylorhalogensubstituted phenyl, and X and X are defined above.

6. A polyether as defined by claim 5 in which A is a radical selectedfrom the group consisting of norcamphanylidene,hexahydro-4,7-methanoindanylidene, hexahydro 4,7methanoindanylmethylene, methylnorcamphanyhnethylene, decahydro 1,4,5,8dimethanonaphthylidene and decahydro l,4,5,8 dimethanonaphthyhnethylenegroups.

7. A polyether as defined by claim 5 wherein mole percent of the radicalX is the divalent radical remaining after the removal of the terminalhydroxyl groups from 4,4'-(2-norbornylidene) dip'henol and 75 molepercent of the radical X is the divalent radical remaining after I H) OHthe removal of the terminal hydroxyl groups from 2,2-bis(4-=hydroxyphenyl) propane.

8. A polyether as defined by claim 5 composed essentially of recurringunits having the formula:

9. A polyether as defined by claim 5 composed essentially of recurringunits having the formula:

10. A polyether as defined by claim 5 composed essentially of recurringunits having the formula:

11. A polyether as defined by claim 5 composed essentially of recurringunits having the formula:

om OH; i

12. A synthetic resinous polyether as defined by claim 5 which is ablock copolymer of from 50 to mole percent of blocks wherein radical Xis derived from Formula I or II and 10 to 50 mole percent of blockswherein radical X is derived from a bifunctional glycol, 21dihydroxylbenzene or a bisphenol of Formula HI.

13. A polyether as defined by claim 12 composed essentially of recurringunits having the formulas:

H CH -CH2CHCH2O WILLIAM H. SHORT, Primary Examiner.

T. D. KERWIN, Assistant Examiner.

